The syntheses of Na(Ttt(Me)) (1), K(Ttt(Me)) (2), K(Btt(Me)) (3), and Na(Btt(Ph)) (4) are reported, where (Ttt(Me))(-) and (Btt(R))(-) (R = Me, Ph) are tri- and di-substituted boron-centered soft ligands; they were produced by the reaction of NaBH4 and KBH4 with the corresponding tetrazole heterocycles: 1-methyl-5-thiotetrazole ((LH)-H-1) and 1-phenyl-5-thiotetrazole ((LH)-H-2). The syntheses of Na(Ttt(Me)) (1) and K(Ttt(Me)) (2) were carried out following Trofimenko's protocol. The anion (Ttt(Me))(-) is a typical Janus scorpionate ligand. Na(Ttt(Me)) (1) and Na(Btt(Ph)) (4) were reacted with Bi(CH3COO)(3) to observe the coordination pattern of these ligands towards bismuth ions. These reactions afforded the complexes [Bi(Ttt(Me))(2)(CH3COO)] (5), [Bi(L-2)(2)](2) (6a, 6b) and [Bi(L-2)(3)] (7). The products were characterized by NMR spectroscopy, elemental analyses and mass spectrometry. Solid state structures were determined by X-ray diffraction of single crystals of 1, 2, 3, 4, 5, 6a, 6b and 7. M(Ttt(Me)) (M = Na (1), K (2)) and K(Btt(Me)) (3) exhibit sheet-like structures. The alkali metal complexes 1-4 dissociate in solution as observed in H-1, C-13 NMR and H-1 diffusion NMR experiments. Negative mode ESI-MS data also indicate the presence of monomers. Both the sodium salts of (Ttt(Me))(-) and (Btt(Ph))(-) as well as the Bi complexes 5 and 7 were investigated by absorption and emission spectroscopy.